Froth flotation of nonsulfide ores with a mixture of oil-soluble and water-soluble petroleum sulfonates



Patented Dec, 23', 1947 rnorn FLOTATION or NONSULFIDE onusv WITH AMIXTURE or OIL-SOLUBLE AND WATER- SOLUBLE PETROLEUM NATES SULFO- RobertBen Booth, Springdale, and Earl Conrad Herkenhofl, Stamford, Conn.,

assignors to American Cyanamid Company, New York, N. Y., a corporationof Maine No Drawing. Application February 4, 1944,

Serial No. 521,130

Claims. (Cl. 209-466) This invention relates to a new class of anionicpromoters for non-sulfide ores and to processes of froth flotation usingthese promoters.

In the past there have been occasional proposals to use as frothflotation promoters certain so-called petroleum sulfonates which arebyproducts in the refining of petroleum lubricating oil fractions bysulfonating agents such as sulfuric acid, oleum, and the like. Becauseof the low price and large supply of these materials in normal times,they would be commercially very desirable. However, the procedures ofusing these compounds in froth flotation have, in the past, achievedlittle, if any, real success. Petroleum sulfonates are normally dividedinto two classes: the oil-soluble variety, which are frequently referredto as mahogany oils or mahogany soaps or mahogany acids and thesubstantially water soluble variety, some of which are usually referredto as green acids. The former have been proposed for use as promotersfor certain members of the class of non-sulfide minerals. When used inthe flotation of iron oxide and garnet, the petroleum sulfonates alonehave not achieved any practical use as recoveries and grades werecommercially not acceptable. In our Patents Nos. 2,410,376 and2,410,377, October 29, 1946, we havedescribed the flotation of ironoxide minerals with oil soluble and water soluble petroleum sulfonates,respectively. The novelty consisted in subjecting the ore to a treatmentwith a strong acid such as, for example, sulfuric acid. The improvementis extraordinary and opens up the field of iron ore beneficiation topractical froth flotation processes using anionic collectors. In asimilar manner, the sulfonates are of great value in the froth flotationof acid treated garnet ores. The garnet flotation is the subject matterof a copending application of Bootls iand Pickens, Ser. No. 502,982,September 18, 1 3.

While for the first time commercially useful grades and recoveries wereobtainable with petroleum sulfonates in the flotation of acid treatediron ores, the individual sulfonates generally left something to bedesired. In general, the oil soluble sulfonates showed somewhat betterresults. However, the products are often more expensive and in somecases less readily available, since they have a variety of uses. Thewater soluble sulfonates also showed good promoting activity but wereopen to the disadvantage that in some cases they were required in largeramounts than in the case of oil soluble sulfonates. In some cases thequality of the froth was also not as good as might be desired.

The present invention is based on the discovery that when mixtures ofoil and water soluble petroleum sulfonates are used much better resultsare obtained than with either used alone in the same amounts. Theresults are quite striking, in some cases permitting better recovery andgrade with less reagents and in other cases giving equal or bettermetallurgy with mixtures containing a. large portion of the cheaperwater soluble sulfonates.

It is not intended to limit the present invention to any theory.Petroleum sulfonates, both 'mahogany and green acids, are not purechemical compounds. They are mixtures of indeterminate chemicalconstitution varying with dif- -ferent oils and with different refiningprocedures.

The tremendous number of variables present. makes any attempt atformulating a theory of action out of the question.

We have found, however, that within wide limits, mixtures of oil solubleand water soluble sulfonates give markedly improved results in the frothflotation of non-sulfide minerals amenable to anionic promoters.Strangely enough, the improvement seems to occur generally with variousmixtures within wide limits in spite of the fact that particularmahogany sulfonates and green acids or other water soluble petroleumsulfonates may vary widely in their 'nature and this is an importantadvantage of the present invention as it creates no problem of supply.

While we have not determined what, it is with certainty, there must besome cooperation between the two typ s of sulfonates because themixtures appear to be applicable over a wide field of froth flotation ofnon-sulfide minerals which respond to anionic collectors. The mostimportant improvements commercially at the moment are iron ore flotationand the flotation of garnet and pebble phospate. However, the reagentmixtures of the present invention are also useful with a wide variety ofnon-sulfide ores. For example, good results are obtained in thebeneficiation of cement rock, limestone, rhodochrosite, coal, barite,scheelite, celestite, cassiterite, kyanite, chromite, fluorite, etc.

The mixtures appear to be generally applicable to non-sulfide oresamenable to anionic flotation but the relative importance of theimprovements obtained will, of course, vary with diife'rent ores.

The mixed sulfonate promoters of the present invention appear to act asimproved sulfonates and not to have changed their basic characteristics.In other words, the mixed promoters of the present invention should beused under the same conditions which have been found to give the bestresults with individual petroleum sulfonates. Thus, for example, in thecase of iron and garnet, the ore should be acid treated beforeflotation. In some cases where the addition of fuel oil and other frothmodifying substances are desirable they should be used with the mixedpromoters of the present invention. However, in the case of fuel oil orother oiling agents it is sometimes possible to dispense with them whena mixture is used or to use smaller amounts. This is not universallytrue but, where applicable, constitutes an additional saving of thepresent invention.

Because of the extremely wide range of characteristics of oil and watersoluble petroleum sulfonates a large number of compositions arepossible. Naturally, different mixtures will give different results, butit is a surprising fact that in very many cases a good mixed promoter isobtained from a mixture of sulfonates neither of which alone would becommercially attractive. In other cases it is possible by the additionof a small amount of effective sulfonate to make a mixed promoter out ofan extremely low grade sulfonate which, although very cheap, ispractically useless alone. This is particularly striking in the case ofsome acid treated iron ore flotations where certain sulfonated residuescan be used in a mixture although alone they are worthless.

In addition to improved metallurgical results and reduced reagentconsumption which are generally obtainable by the use of the presentinvention, the mixtures in many cases show improved general flotationcharacteristics. Thus, for example, the quality of the froth is oftenbetter when a mixture is used than when either one is used alone and themixtures in general are more readily dispersed in water. Some are soreadily dispersed that they may be fed in water solution or dispersion,thus simplifying the feeding of the reagent. In many cases markedlyimproved feeding, distributing and froth characteristics are obtained inmixtures which contain a relatively small proportion of one or the otherof the two kinds of sulfonates.

In general it is an advantage of the present in vention that theproportion of the two kinds of sulfonates may be varied within widelimits. Many of the best mixtures are those in which the two sulfonatesare present in substantially equal amounts. However, under favorablecircum stances and particularly in the froth flotation of acid treatediron ore the range may be from 25 parts of oil soluble sulfonate to 1part of water soluble sulfonate to 1 part oil soluble sulfonate to 25parts water soluble sulfonate. However, it is not preferred in generalto use the extremes and the preferred range is from 10 parts of oilsoluble sulfonate to 1 part water soluble to 1 part oil so]- uble to 10parts water soluble. In the case of certain sensitive mixtures and incertain flotation operations decrease in efiiciency may even be notedwith ratios as low as 6 to l. The wide range permits formulation ofmixed promoters according to the present invention having desiredcharacteristics and particularly it is possible in many cases to use amixture containing a small portion of more expensive sulfonate and alarge portion of cheap sulfonate. The wide range of proportions are alsovaluable as safety factors because commercial petroleum sulfonates arenot always uniform and may vary from day to day.

Throughout the specification and claims the term petroleum sulfonate" isused in the loose sense in which this term is employed in the petroleumart. While, as has been stated above the constitution of varioussulfonates is not accurately determined, it is probable that much of thecombined acid is present in the form of the sulfate group rather thansulfonate group. Many unsaturated hydrocarbons of lubricating oil stocksin the refining procedur give rise to sulfuric acid half-esters. This isparticularly true in the case of some.of the water soluble sulfonates.,However, the art uses a single term to cover the products obtained andthis term will be used throughout the specification and claims, it beingunderstood that the sulfur-containing acid groups ar not limited tosulfonic groups. While the term "petroleum sulfonate is used loosely asfar as the sulfur containing acid groups are concerned, it is limited toproducts obtained by refining petroleum lubricating oil stocks withsulfonating agents. It does not include acid sludges obtained by thesulfuric acid treatment of fuel fractions such as kerosene.

The petroleum suifonates of commerce are not pure chemical compounds.Thus, for example, the oil-soluble petroleum sulfonates are commerciallysold in the form of dispersions in unsuifonated oil and the commercialproducts referred to in the application are of this nature. Watersolublepetroleum sulfonates are also for the most part mixtures and are notchemically pure substances. Throughout the specification and claims theterm petroleum sulfonate is used to include the impure commercialproducts which are customarily sold.

It is an advantage of the present invention that in general the frothflotation procedure is not materially changed by the use of thepromoters of the present invention and other adjuncts such as dispersingagents, depressants and the like will normally be employed where theiruse with a particular or has been found to be generally desirable. Insome cases, notably in the addition of oiling agents such as hydrocarbonoils, glyceride oils and the like, optimum conditions will vary withdifferent mixtures of sulfonates and often are not identical withoptimum conditions for individual components. respect. the mxedpromoters of the present invention behave in a manner which is common innon-sulfide flotation. In the more specific descriptions in the examplesin every case optimum conditions are used. The determination of optimumconditions, as is well known, is not difficult or critical but should bemade in every case as is standard practice in the art. It is a furtheradvantage of the present invention that the general behavior of thefroth flotation is similar to known froth fiotations of the same ore andthe operator does not have to learn new techniques.

Since many of the various oil soluble and water soluble petroleumsulfonates are of indeterminate structure they cannot be identified bychemical formula and, therefore, in the examples the products will beidentified by their trade names and source of supply. This is the onlymethod of identification practical with petroleum sulfonates and itshould be understood that in some cases sulfonates having practicallythe In this.

does not appear to be adversely affected by the method of feeding thereagents so long as thorough mixing with the ore is effected.

The invention will be described in greater detail in conjunction withthe following specific examples which show results obtainable in thefroth flotation of six types of non-sulfide ores.

Example 1 A Minnesota iron ore, a. washer reject. containing about 30.5%Fe, was deslimed and the pulp treated with acid, promoter and, in somecases, fuel oil, the treatment being at high solids (60-70%) which hasbeen found to be the most effective conditioning for this type of ore.After conditioning was completed, the thick pulp was diluted to frothflotation density and was subjected to a rougher float and followed by asingle cleaning using Fagergren flotation machines. The results of thetests giving the amount of reagent used appear in the following table ofmetallurgical results. In every case about 2.6 lbs. per ton of sulfuricacid was used and the pH of the rougher tailing was in the neighborsamecharacteristics may be supplied by different hood of 3.0.

Oil-Soluble Petroleum Sulionatc Water-Soluble Petroleum SullonateConcentrate Rgh Tailing Lbs./'Ion T Lb [T 1* Lb T Fuel on r A$50M t r iP5555333,

ype s. on ype s., on or .en 0 e,

Fe Per Cent Fe Clgol socgglni Sulionate (Standard Oil 2. 3i None None60. 21 83. 13 6. 48

Do 2v iii .do 1.17 59. 94 93. 41 2.

Do U. 95 .do 0.95 63. 34 67. 84 10. 42

None Urecn Sulionic Acids-Neutralized 8. 2. 78 5B. 59 93. 90 3. 51

(Sun Oil Co.).

Calol Sodium Sultanate (Standard Oil 1. 16 60. 48 83. 66 6. 27

Co. of Cal.).

Oronite #2 (Granite Chem. Co.)... 4. 15 59.01 96. 63 1.73

None 60. 89 92.61 3. ll

. do None 64.50 48. 29 i6. 44

. U reen Sulfonic Acids-Neut.-.. 2. 60. 35 94. 89 2. 43

None None 63. 32 25. 29 24. 57

.do None A N 0 Useful Promotion Green Sulionic Acids-Neat 1.61 1.89 61.02 I 91. 00 I 3. 78

manufacturers under difierent names. However, in the specific exampleswhich are to follow, numerous types of sulfonates have been used and notwo sulfonates are of identical flotation characteristics. The petroleumsulfonates of the examples are, however, all true petroleum sulfonates.that is to say, products obtained from the refining of lubricating oilfractions with sulfonating agents.

It is an advantage of the present invention that the feeding of themixed sulfonates is not critical. They may be mixed and fed as amixture. Water soluble and oil soluble sulfonates may be fed separatelyand one, or both, or the mixture may be dissolved in oil or dispersed inwater. When a mixture is being dispersed it is a further advantage thatsome of the water soluble sulfonates act as dispersing or solubilizingagents for the oil soluble sulfonates.

The dispersing effect of some of the water soluble sulfonates representsan operating advantage asdispersions can be made up in a much shortertime and, in some cases, in more concentrated form. Within wide limitsthe metallurgy It will be noted that in every case the same or bettergrade and recovery is obtainable with a mixture in amounts considerablysmaller than that required if water soluble sulfonates alone are usedand in some cases materially smaller than when oil soluble sulfonatesalone are employed. In each case the amount of fuel oil represents thatwhich will give optimum results with the particular reagent combinationemployed.

Example 2 Oil-Soluble Petroleum Sullonate Water-Soluble PetroleumSulloxmte Concentrate F Ta ling Lbs. Ton Fue on Assay Dlstrib. 4 35.Type Lbs/Ton Type Lbs./Ion Per Cent 01 e, 9

Fe Per Cent Rea ent 407 (Sherwood Refg Co.) None 61.29 90.95 1.62 None61. 97 86. 49 1. 89 N one.- 1. 29 58. 86 95.82 0. 81 o... 0. 63 76.16 2.90 Rea ent: 40 None 57 65 96. 13 0. 81 in None 59.41 96.83 0.58Petroleum Sullonotes (Shell 01100.)" 1.60 01.16 88.55 1. 62 None SogwsalGr)een Acids(Sonneborn 2.10 1.78 59.81 95.08 1.08

ons, nc.

Do .110 0.90 0.84 61. 49 95. 96 0.81 Do... 0. 56 0. 49 61. 95 91.14 1.27 Petroleum Sulfonotcs 0.85 2.22 50.00 96.13 0.81 D 0. 57 1. 51 61.0395. 49 0.69 None 62. 70. 70 3. 65

None N 0 Useful Promotion 1. 29 58. 86 95. 82 0. 81 o 0. 63 61. 95 76.16 2. 90 Crude Naphtha Sullonic Soap None 58.19 97. 51 0. 54 Eldrol(Penna. Oil Prod. Rcfg None 6210 89.48 1. 79 ])o None 62. 37 83. 76 2.43 4.08 43. 61 25.05 13. 50 None 62. 10 85. 69 2. 03 None 62.10 92. 631.08 1 29 58.86 95.82 0.81 0. 63 61. 95 76.16 2. 90 0 None 81. 70 94. 0.95 SP-312 (Stanco None 62.37 89.08 1.22 None 5. 83 60. 89 93. 39 0.54 1.48 61. 43 95.12 0.68 2. 08 60. 16 92.08 0.92 o 3.64 60.50 90.22 0.81Glgelncsulfonic AcidsNeut. (Sun 2.86 3.24 61.88 89.64 1.84

Oronite #2 0.24 .do 2.71 3 35 58. 79 97.90 0.35 None NeutralizedWater-Soluble Terry 12. 20 1.50 56, 39 91.21 1. 9 Fraction from GreenSuifonic Acids (Sun Oil Co.).

Oronite #2 1.47 do 1.47 3. 83 60.85 95.76 0.69 N one AcidicWater-Soluble Tarry n 9.38 1. 55 57. 29 92, 56 1. 62 from Green SulfonicAcids (Sun 01100.). Oronite #2 1.50 (10 1.50 3. 42 60. 73 97.10 0.46

It W111 be noted that the sulfonate mixtures Example 3 of the presentmventlon produce 1n every case The ore of Example 1 was conditioned asiron concentrates of merchantable grade with scribed therein and wassubmitted to a series excellent recoveries in spite of the fact that theof tests wlth mlxtures of Water Soluble and 011 soluble sulfonates invarying proportions. The ole 15 very low the results are metallurgicalresults appear in the following as good or better Wlth thls low gradeore as table. In every case the amount of sulfuric acid with t e highergrade ore of Example 1. Possiused was about 2.6 lbs. per ton of ore andthe bility of treating such low grade ores Is an imamount of fuel 0 1chosen w the optlmum r portant advantage of the present invention. thegiven Yi m i The pH of the rougher tailing remamed shghtly below 3.0.

Sulfonate Mixture Used Lbs/Ton Concentrate R h g w s 1 bl s It t 1Oil-Soluble Sulfonate atero u e u one. o ssay Assay Assay Per Cent :53;Per Cent Per Cent Distrib. S Type Parts Type Parts 6 H501 F6 Oronite #2(Oronite Chem. Co.) 4. 12 26 40 12. 56 99 7. 33 D0 4.12 4. 15 59. 01 11.54 96. 63 1. 73 (lo 1. 1. 59 03. 69 4. 45. 01 15. 52 Green SulfonieAcidsNeut- 100 8. 40 2.78 58. 59 12.00 93. 3. 51

ralized (Sun Oil Co.)

4. 20 1. 39 60. 35 9. 48 78. 08 7. 97 3. 14 3. 23 59. 47 9. 74 96. 35 1.73 3. 14 3. 34 60. 04 9. 72 96. 56 1. 61 3. 14 3. 69 60. 96 8.54 95. 072. 30 3. 14 3. 69 60. 50 9. 06 90.11 1. 61 3. 14 2. 98 59. 58 10. 56 97.03 1. 38 3. 14 4. 01 59. 24 10.84 97. 37 1. 27 3. 14 3. 69 60. 39 9. 0296. 61 1. 84 3.14 3. 60 60.16 9. 44 95. 91 2.19 3. 14 3. 23 59. 81 9. 5096. 72 1. 73 3. 14 3. 23 59. 58 10. 60 96. 52 1. 84 3. 14 3. 23 50. 939. 90 96. 43 1. 73 3. 14 3. 23 58. 78 11. 22 96. 18 1. 84 3. 31 None 02.30 (i. 98 87. 79 4. 52

2. 10 None (14.62 4. 60 31. 53 22. 23 2. 07 1. 82 62. 88 6. 38 54. 0518. 64 2. 64 1. 86 59. 41 11. 30 94. 90 2. 32 2. 06 1. 81 50. 98 10. 2494. 41 2. 66 1. 23 0.91 64. 50 5.14 14. 50 21. 54 2. 06 1. 81 01. 26 3.52 94. 81 2. 08 2. 06 1. 81 61. 7. 74 89. 98 3. 71 2.10 1.11 62.42 7.0288.22 3.82 2.06 0. 54 03. 46 5. 88 74.83 8.11

per ton.

2,4aa2ss Example 4 A low grade iron or containing hematite, siderite,and goethite assaying about 16% Fe was ground and then prepared asdescribed in Example 1. The reagents were added as a 12% aqueousdispersion. The sulfuric acid was just under 2 lbs. per ton and the pHof the rougher tailing just below 3.0.

Promoter Used Concentrate I JFbsJ Tilting, on ssay Lbs. Fuel gg gg PerType Per Oil Cent Per Cent Ton Fe Fe Cent Eldrol (il-Sol.-Penna.

Oil Prod.) 2. 86 None 56.36 75.17 4. 14 SP-702 (Water-Sol.

StaneoDistrib.,Inc.) 2.26 1.24 52.22 89.23 1.73 1:1 Mixture of Eldroland SP-702 2.35 0.64 54.17 88. 86 1. 84 Do 1.98 None 56. 36 73. 10 3. 91

These tests with respresentative mixed sulfonates show the effectivenessof the new reagent on a very refractory low grade iron ore. The resultsare, of course, not quite as good as with the more easily floatable oresof Examples 1-3 but demonstrate the fact that even extremely refractoryores may be treated with the mixed promoters of the present invention toobtain reasonable recoveries in fairly high grade products.

Example 5 l A high grade table concentrate containing principallymagnetite, martite and silicate gangue and analyzing about 66% Fe wasconditioned and floated as described in Example 1. The reagent was addedas a 6% aqueous dispersion. The amount of sulfuric acid was 4 lbs. perton and the amount of fuel oil just under 2 lbs. The pH of the roughertailings was about 2.5. The following table tells the metallurgicalresults.

It will be apparent that although the water soluble acids gave a verypoor recovery with only slight increase in grade, the mixture gave thesame or slightly higher grade with almost as good recovery as the oilsoluble sulfonate alone. This test is particularly severe because theoil soluble sulfonate was one of the very best when used alone and thewater soluble sulfonate gave no useful result even when used in muchlarger amounts.

Example 6 A garnet ore from the northeastern United States, containingabout 26% garnet mainly as almandite with a hornblende, quartz,feldspar, biotite and pyrite gangue, was ground to flotation size anddeslimed. The deslimed ore was conditioned with 5 lbs. per ton ofsulfuric acid and petroleum sulfonate in the amount of 1.0

lb. per ton. The sulfonates used here were Calol Sodium Sulfonatediluted with 10% secondary butyl alcohol and a typical green acid fromthe Sun Oil Company. Flotation was effected in a Fagergren flotationmachine, a rougher float being taken and the rougher concentrate cleanedafter conditioning with 0.5 lb. per ton of sulfuric acid. The cleanerconcentrate was then conditioned with 1 lb. per ton of sulfuric acid andrecleaned. The following table gives the results of the three tests.

In the case of test 2, cleaning was omitted as the rougher concentratewas so poor and the recovery so low that the procedure was not prac-vtical. The marked increase in grade obtained with mixed sulfonates isparticularly important with garnet because the ore is relatively cheapand the demand is for a very high grade concentrate. In this type oi.flotation, therefore, the grade is considerably more important than therecovery. A higher grade was made with about 6% increase in recovery inthe case of the mixture of sulfonates, as compared to the resultsobtained with the better of the components of the mixture.

Example 7 A rake classifier product of pebble phosphate from theLakeland, Florida district, assaying about 36.5% B. P. L., wasconditioned with 0.75 lbs. per ton of a 1:1 mixture of neutralized greensulfonic acids and Calol sodium sulfonate and with 0.99 lb. per ton oftalloel together with 4.86 lbs. per ton of fuel oil. Conditioning waseffected at high solids in the common manner but differed from the usualFlorida practice in that the anionic promoter was used without anycaustic soda. After diluting to flotation density the pulp was floatedin a Fagergren flotation machine, a rougher concentrate was obtained andwas then cleaned. Separate tests were made with each of the componentsof the mixture described. The green acids alone gave no flotation eitherin the amount present in the mixture, 0.37 lb. per ton, or in the amountof 0.75 lb. per ton. The following table shows metallurgical results.

8311 1 l Mixture Product um Sultanate Cleaner Cone, Per Cent BPL Assay77. 42 78. 73 Cleaner ionc. Ier (mttlrgsloliligfiatyisn. 3. 21 3. 65

. s r u- Middling Product, Per Cent BPL Assay. 39. 52 41. 58 MiddiingProduct, Per Cent BPL Distribution 2 48 5. l0

Tailiu Per Cent BPL Assay 14. 80 6.10 Telling: Per Cent BPL Distribution2a 62 0. 15

It will be noted that while commercially useful results are obtainedwith Calol sodium sulfonate alone, substantially the same grade wasobtained with a marked increase in recovery when the mixture was used.The flotation feed contained considerably more slimes than are usual inflotation operations on this ore in Florida, and it is to be noted thatthe mixed sulfonates appear to show low slime sensitivity, an importantpractical advantage.

In the examples dealing with iron ore and arnet ore sulfuric acid hasbeen described as the acid treating agent. As described in our copendingapplications referred to above, sulfuric acid gives excellent resultsand its cheapness makes it the preferred material. However, other strongacids which do not contain anions that adversely affect flotation givesimilar results and it is an advantage of the present invention that themixed sulfonates are likewise not sensitive to the particular strongacid used in the present treatment of the ore. Instead of a strong acidcertain strong' acid salts such as sodium bisulfate and the like may beemployed. In the foregoing examples the mixed sulfonates of the presentinvention have been used as promoters in froth flotation processes. Thisis the most important practical field for the compositions and the onein which they show their greatest advantage. However, it should beunderstood that the mixed sulfonates of the present invention are also'usable in other wet separation processes involving agglomeration suchas tabling, belt tabling, film flotation and the like.

In the claims the term oxidized iron ores" is used in its commonlyaccepted meaning to include not only iron oxide ores such as thosecontaining magnetite, hematite, etc., but also hydroxides, carbonates,etc.

We claim:

1. A method of beneflciating a non-sulfide ore amenable to anionic frothflotation which comprises subjecting an aqueous pulp of the ore to frothflotation in the presence of a collector for the non-sulfide material,said collector containing as its essential collecting component amixture of 496% of oil soluble petroleum sulfonates and 964% of watersoluble petroleum sulfonates and recovering a concentrate rich in thedesired non-sulfide material and tailing poor in the same,

the petroleum sulfonates being obtained in the refining of petroleumlubricating oils.

2. A method of beneficiating a' non-sulfide ore amenable to anionicfroth flotation which comprises subjecting an aqueous pulpof the ore tofroth flotation in the presence of a collector for the non-sulfidematerial, said collector containing as its essential collectingcomponent a mixture of 10-90% of oil soluble petroleum sulfonates and90-10% of water soluble petroleum sulfomates, and recovering aconcentrate rich in the desired non-sulfide material and tailing poor in12 the same. the petroleum sulfonates being obtained in the refining ofpetroleum lubricating oils.

3. A method of beneflciating an acid treated oxidized iron ore whichcomprises subjecting an aqueous pulp of the ore to froth flotation inthe presence of a collector for the acid treated iron ore, saidcollector containing as its essential collecting component a mixture of4-96% of oil soluble petroleum sulfonates and 96-4% of water solublepetroleum sulfonates, and recovering a concentrate rich in iron andtailing poor in iron, the petroleum sulfonates being obtained in therefining of petroleum lubricating oils.

4. A method of beneflciating an acid treated oxidized iron ore whichcomprises subjecting an aqueous pulp of the ore to froth flotation inthe presence of a collector for the acid treated iron ore, saidcollector containing as its essential collecting component a mixture of10-90% of oil soluble petroleum sulfonates and -10% of water solublepetroleum sulfonates, and recovering a concentrate rich in iron andtailing poor in iron, the petroleum sulfonates being obtained in therefining of petroleum lubricating oils.

5. A method of beneficiating an acid treated garnet ore which comprisessubjecting an aqueous I pulp of the ore to froth flotation in thepresence of a collect-or for the acid treated garnet ore, said collectorcontaining as its essential collecting component a mixture of 4-96% ofoil soluble petroleum sulfonates and. 96'-4% of water soluble petroleumsulfonates, and recovering a concentrate rich in garnet and tailing poorin garnet, the petroleum sulfonates being obtained in the refining ofpetroleum lubricating oils.

6. A method of beneflciating an acid treated garnet ore which comprisessubjecting an aqueous pulp of the ore to froth flotation in the presenceof a collector for the acid treated garnet ore, said collectorcontaining as its essential collecting component a mixture of 10-90% ofoil soluble petroleum sulfonates and 90-10% of water soluble petroleumsulfonates, and recovering a concentrate rich in garnet and tailing poorin garnet, the petroleum sulfonates being obtained in the refining ofpetroleum lubricating oils.

7. A method of beneflciating a sulfuric acid treated oxidized iron orewhich comprises subiecting an aqueous pulp of the ore to froth flotationin the presence of a collector for the sulfuric acid treated iron ore,said collector containing as its essential collecting component amixture of 4-96% of oil soluble petroleum sulfonates and 964% watersoluble petroleum sulfonates, and recovering a concentrate rich in ironand tailing poor in iron, the petroleum sulfonates being obtailiged inthe refining of petroleum lubricating o 8. A method of beneficiating asulfuric acid treated oxidized iron ore which comprises sub- .lecting anaqueous pulp of the ore to froth flotation in the presence of acollector for the sulfuric acid treated iron ore, said collectorcontaining as its essential collecting component a mixture of 10-90% ofoil soluble petroleum sulfonates and 90-10% of water soluble petroleumsulfonates, and recovering a concentrate rich in iron and tailing poorin iron, the petroleum sulfonates being obtained in the refining ofpetroleum lubricating oils.

9. A method of beneficiating a sulfuric acid treated garnet ore whichcomprises subjecting an aqueous pulp of the ore to .froth flotation inthe Presence of a collector for the sulfuric acid treated garnet ore,said collector containing as its essential collecting component amixture of 4-96% of oil soluble petroleum sulfonates and 96- 4% of watersoluble petroleum sulfonates, and recovering a concentrate rich ingarnet and tailing poor in garnet, the petroleum sulfonates beingobtained in the refining of petroleum lubricating oils.

10. A method of beneficiating a sulfuric acid treated garnet ore whichcomprises subjecting an aqueous pulp of the ore to froth flotation inthe presence of a collector for the sulfuric acid treated garnet ore,saicl collect-or containing as its essential collecting component amixture of 10-90% of oil soluble petroleum sulfonates and 90-10% ofWater soluble petroleum sulfonates, and recovering a concentrate rich ingarnet and tailing poor in garnet, the petroleum sulfonates beingobtained in the refining of petroleum lubricating oils.

ROBERT BEN BOOTH. EARL CONRAD HERKENHOFF.

14 REFERENCES CITED The following references are of record in thefile ofthis patent:

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